Insights into the formation and degradation mechanisms of methylenedinitramine during the incubation of RDX with anaerobic sludge

In an earlier study, we reported that hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegraded with domestic anaerobic sludge to produce a key RDX ring cleavage intermediate that was tentatively identified as methylenedinitramine (O2NNHCH2NHNO2) using LC/MS with negative electrospray ionization (ES-). Recently, we obtained a standard material of methylenedinitramine and thus were able to confirm its formation as the key initial RDX intermediate. In water alone or in the presence of sludge, methylenedinitramine decomposed to N20 and HCHO. Only in the presence of sludge HCHO converted further to carbon dioxide. To test our hypothesis that water was involved in the formation of methylenedinitramine during incubation of RDX with sludge, we allowed the energetic compound to biodegrade in several D2O/H2O solutions (90, 50, and 0% v/v). We observed three distinctive deprotonated or dedeuterated mass ions at 135, 136, and 137 Da that were attributed to the formation of nondeuterated (H-methylenedinitramine), monodeuterated (D1-methylenedinitramine), and dideuterated methylenedinitramine (D2-methylenedinitramine), respectively. Two controls were prepared in D2O both in the absence of sludge; the first contained methylenedinitramine, and the second contained RDX. Neither control produced any deuterated methylenedinitramine, thus excluding the occurrence of any abiotic D/H exchange between D2O and either methylenedinitramine or RDX. The results supported the occurrence of an initial enzymatic reaction on RDX, yet they did not provide compelling evidence on whether methylenedinitramine was an initial RDX enzymatic hydrolysis product or simply formed via the spontaneous hydrolysis of an anonymous initial RDX enzymatic product.     

Comparison of direct-sequence impulse radio and direct-sequence ultra-wide bandwidth in multi-user interference

A new ultra-wide bandwidth communication system using both a time-hopping (TH) sequence and a direct spreading sequence, called direct-sequence impulse radio (DS-IR), has recently been proposed. An exact analysis to evaluate the bit error rate (BER) performance of this new scheme in multi-user interference (MUI) is provided. On the basis of this new analysis, ultra-wideband communication systems employing TH, direct-sequence and the newly proposed DS-IR schemes operating in MUI are accurately compared in terms of the BER. Our results indicate that DS-IR outperforms the TH binary phase-shift keying (BPSK) system. However, its performance is poorer than the performance of the conventional full-duty direct sequence BPSK system. Compared with the low-duty direct sequence BPSK system, DS-IR achieves a better error rate performance for medium and large signal-to-noise power-ratio values.     

Crystallization of polylactide films: An atomic force microscopy study of the effects of temperature and blending

Surface crystallinity on films of poly(l-lactide), poly(l/d-lactide) and their blends with poly(d-lactide) was studied. The isothermal spherulitic growth rate and its dependence on temperature were studied using tapping mode atomic force microscopy and ex situ isothermal crystallization. Using this technique, it is possible to extend spherulitic growth rate measurements to the region of significantly higher supercooling where nucleation concentration makes the use of in situ hot stage optical microscopy impossible. It was confirmed that while a poly(l/d-lactide) copolymer exhibits the typical “bell” shaped crystallization rate–temperature dependence, poly(l-lactide) exhibits a nonsymmetrical behavior having two crystallization rate maxima at 105 °C and 130 °C. As expected, the spherulitic growth rate of poly(l-lactide) was significantly higher than that of poly(l/d-lactide). The different types of crystalline formations exhibited at the surface of polylactide films are shown and discussed. The crystalline long spacing of poly(l-lactide) was also measured directly using tapping mode AFM and was found to be 19 nm at 165–170 °C. At low supercooling, several different scenarios of individual crystal formation were observed: purely flat-on stacks, purely edge-on stacks and scenarios where edge-on crystals flip to flat-on crystals and vice versa, where flat-on crystals yield edge-on sprouts. The preferred direction of growth of lamellae of both poly(l-lactide) and poly(d-lactide) was found to be counter-clockwise relative to the free surface.Finally, the crystallization kinetics of blends of poly(l-lactide) and poly(l/d-lactide) with poly(d-lactide) were studied. In such blends a triclinic stereocomplex crystalline structure forms between chains of opposite chirality and a pseudo-orthorhombic α-crystal structure forms between chains of like chirality. The presence of the stereocomplex crystals affects both the nucleation and the growth of the α-crystals. In fact depending on the stereocomplex content and the crystallization temperature the α-crystallization can either be enhanced or be inhibited. Interestingly it was found that the presence of the stereocomplex had a much stronger effect on the α-crystallization of poly(l/d-lactide) than on the α-crystallization of poly(l-lactide).     

Feeding co-extruded flaxseed to pigs: Effects of duration and feeding level on growth performance and backfat fatty acid composition of grower–finisher pigs

To examine the effect of co-extrusion on subsequent n-3 fatty acids in pig tissues, 8 pigs (barrows and gilts) were assigned to either a control treatment or one of nine treatments arranged in a 3 × 3 factorial design with 3 levels of co-extruded flaxseed (5%, 10% and 15%) and 3 durations of feeding (4, 8 and 12 weeks). Feed conversion improved slightly (P = 0.01) with increasing dietary flaxseed but feeding flax for more than 8 weeks reduced average daily gain (P = 0.02). In general, the duration and level of co-extruded flaxseed feeding affected (P < 0.05) most fatty acids except for 22:6n-3 (P > 0.05). Increasing the duration of flax feeding led to significant quadratic effects in backfat 18:3n-3 (P < 0.001) and total n-3 fatty acids (P = 0.002) when feeding 5% co-extruded flaxseed. Those increases were linear (P < 0.001) when feeding 10% and 15% co-extruded flaxseed. Consequently feeding higher levels of flax for shorter periods vs. lower levels for longer periods appears to be more efficient at increasing n-3 fatty acids in pig backfat, but increases appeared to be less consistent. Moreover the addition of a 50:50 mix of extruded flax/peas to pig diets provided a highly available source of 18:3n-3 yielding n-3 fatty acid enrichments in backfat comparable to studies where extracted flaxseed oil was fed. Feeding flax co-extruded with field peas can be used to optimize consistent enrichments of n-3 fatty acids in back fat and relatively small amounts of this fat could be used to manufacture pork products to meet Canadian standards for n-3 fatty acid enrichment.     

Effects of molecular weight,stereo configuration of PLA,and processing on the dispersion of multiwalled carbon nanotubes and properties of corresponding nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were dispersed and distributed via a co-rotating twin-screw extruder (TSE) in high (h)- and low (l)-molecular-weight amorphous and semicrystalline polylactides (PLAs) (aPLA and scPLA, respectively). Effects of PLA molecular weight and D-lactic acid equivalents content (D-content), as well as processing parameters, were examined on the MWCNT dispersion quality in PLA. The effectiveness of the MWCNT dispersion in various PLA matrices was investigated using scanning electron microscopy (SEM) and small-amplitude oscillatory and transient shear flow rheometry in the molten state. The results showed a better dispersion of MWCNTs in the low-molecular-weight PLA grades (aPLAl and scPLAl). In addition, better MWCNT dispersion was observed in aPLA grades when processed at a higher temperature of 190°C than at 150°C. At 150°C, while MWCNT bundles in aPLAl could be broken down, a good dispersion could not be achieved in aPLAh due to the lower molecular mobility at such a temperature. The electrical conductivity of the samples was also shown to increase as the MWCNT dispersion was improved. The existence of crystallites in scPLA-based nanocomposites, however, disrupted the connectivity of the MWCNTs and decreased the final electrical conductivity. The lower molecular weight aPLAl prepared at 190°C showed the highest electrical conductivity (~10⁻⁵ S/m) at a low loading of 0.5 wt.% MWCNTs.